CN108671959A - Difunctional organic porous material and preparation method thereof - Google Patents
Difunctional organic porous material and preparation method thereof Download PDFInfo
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- CN108671959A CN108671959A CN201810700073.XA CN201810700073A CN108671959A CN 108671959 A CN108671959 A CN 108671959A CN 201810700073 A CN201810700073 A CN 201810700073A CN 108671959 A CN108671959 A CN 108671959A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000013309 porous organic framework Substances 0.000 claims abstract description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 bromine anions Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical class BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 125000001246 bromo group Chemical group Br* 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000013308 plastic optical fiber Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical class OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 5
- 150000004694 iodide salts Chemical class 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000006352 cycloaddition reaction Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BDGCAHYGTNRIOD-UHFFFAOYSA-N 2,5-dibromo-1h-pyrrole Chemical class BrC1=CC=C(Br)N1 BDGCAHYGTNRIOD-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
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- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
Abstract
The present invention provides a kind of no metal, environmental-friendly difunctional porous organic frame catalysis material and preparation method thereof, belongs to organic porous material preparation method field.The preparation method of the difunctional porous organic framework materials is, polymerisation occurs by two kinds of organic construction units first and connects the porous organic frame substrate formed with pyridine site, it is modified after carrying out bromoacetic acid to it again, obtains carboxylic acid site and bromine anions site.The present invention's can efficiently be catalyzed CO without the difunctional porous organic framework materials of metal under the conditions of without existing for homogeneous synergistic catalyst2It is reacted with epoxide, generates cyclic carbonate；The difunctional porous organic framework materials of the present invention have preparation method simply easily operated, and material non-toxic is environmentally friendly, catalytic performance high repeatability and other advantages.
Description
Technical field
The present invention relates to the interleaving techniques such as organic chemistry, materials chemistry, catalytic chemistry fields, and in particular to difunctional organic
Porous material and preparation method thereof.
Background technology
Human being's production and activity generate a large amount of carbon dioxide (CO2) it is generally considered a kind of greenhouse gases, face ring
The influence in border and damaging property of the ecological balance.But CO2It is also a kind of nontoxic, non-combustible, rich reserves important C1 moneys
Source can be converted to a variety of raw materials of industry with economic value.Therefore, compared to CO2Carry out simple absorption capture
Processing, with CO2For raw material, chemical conversion is carried out to it and is more of practical significance and economic value.But due to CO2With higher
Thermodynamic stability and kinetic inertness, it is not easily-activated, in reaction process usually require high temperature, high pressure or using catalyst with
Reduce energy barrier needed for reaction.Therefore, the selection of catalyst is particularly important, and efficient catalyst can not only improve CO2Conversion
Rate can also reduce the temperature and pressure needed for reaction process, to which cost-effective, reduction is to consersion unit requirement.So opening
It is to efficiently use CO to send out catalyst efficient2Key.
Porous organic frame (Porous Organic Frameworks, POFs) material as a kind of novel porous materials,
Have the characteristics that large specific surface area, aperture structure are adjustable, functionality is various, in gas absorption/separation, energy stores, matter
The numerous areas such as sub- conduction, detection, pollutant process show excellent application performance.Since POFs materials have functional site
Diversity and high reaction activity, POFs materials are applied to as a kind of catalysis material in a variety of catalysis reactions.Currently, with
POFs materials have been able to realize catalysis CO as catalyst2It carries out cycloaddition reaction and generates the raw material of industry with economic value
Propene carbonate.But developed POFs catalyst system and catalyzings are using toxic heavy metal as lewis acid position, or need that collaboration is added
Catalyst could realize catalyzed conversion.These disadvantages cause the increase of industrial cost, are unfavorable for energy conservation and environmental protection.Therefore, it prepares
Heavy metal free, it is environmental-friendly and can it is mild, do not need existing for synergistic catalyst under the conditions of can efficient catalytic CO2Conversion
POFs catalysis materials there is practical significance.
Invention content
The purpose of the present invention is to solve existing porous organic frame catalysis materials in catalysis CO2Cycloaddition reaction mistake
Needed in journey using toxic heavy metal as lewis acid, need synergistic catalyst and high temperature and pressure the problem of, and provide a kind of nothing
Metal, environmental-friendly difunctional porous organic frame catalysis material and preparation method thereof.
Present invention firstly provides a kind of difunctional porous organic frame catalysis materials, shown in structural formula such as formula (I)：
The present invention also provides the preparation methods of the difunctional porous organic frame catalysis material, include the following steps：
Step 1：Four (4- alkynyls tetraphenyl) methane, 2,5- dibromo pyridines, tetrakis triphenylphosphine palladium, cuprous iodide is molten
In the in the mixed solvent of n,N-Dimethylformamide (DMF) and triethylamine, reaction system evacuates nitrogen charging processing by freezing three times
Afterwards, it is heated at 60~100 DEG C and reacts 1~4 day, obtain mixed liquor；Four (4- alkynyls tetraphenyl) methane, 2,5- dibromo pyrroles
Pyridine, tetrakis triphenylphosphine palladium, cuprous iodide, DMF and triethylamine molar ratio be 1:1~4:0.015~0.03:0.015~
0.03:100~300:50~80.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 3~5 times, and the organic matter and catalyst that can be dissolved are removed, 80~120 under conditions of vacuum degree is 133Pa
DEG C vacuum drying 12~15 hours, obtain the porous organic framework materials (POF-PN) containing pyridine site.
Step 3：At room temperature, the POF-PN is dispersed in toluene solution, is added under nitrogen protection and stirring condition
Bromoacetic acid is heated at 50~90 DEG C and reacts 1~4 day；It is cooled to room temperature, solid product methanol, acetone wash 3 after filtering
~5 times, be dried in vacuo 10~15 hours for 80~100 DEG C under conditions of vacuum degree is 133Pa, obtain containing carboxylic acid and bromine the moon from
The difunctional porous organic frame catalysis material (POF-PNA-Br in site of son-)；The molar ratio of POF-PN, bromoacetic acid and toluene solution
It is 1:1~5:200~500.
The molar ratio preferably 1 of described four (4- alkynyls tetraphenyl) methane, 2,5- dibromo pyridines：2~3.
Preferably 80~90 DEG C, 2~3 days of the step 1 reaction temperature, time.
The molar ratio of the POF-PN, bromoacetic acid and toluene solution preferably 1:2~3:280~400.
Preferably 60~80 DEG C, 1~2 day of the step 2 reaction temperature, time.
The difunctional porous organic frame catalysis material POF-PNA-Br-It is catalyzed CO2With the reaction formula of epoxide
For：
Wherein, R=CH3, CH2Cl, CH2CH3Or CH2CH2CH2CH3。
Two kinds of porous organic framework materials POF-PN and POF-PNA-Br prepared by the above method-, microcellular structure is all had,
With higher specific surface area, respectively 602m2g-1And 288m2g-1.Wherein, POF-PNA-Br-Make with carboxylic acid group (- COOH)
Be lewis acidity site position and bromide ion as nucleopilic reagent site, and with preferable thermal stability and it is good chemistry surely
It is qualitative, it can be catalyzed CO in mild and do not need existing for homogeneous synergistic catalyst under the conditions of2Ring is carried out with epoxide to add
At reaction, cyclic carbonate is generated.
Heavy metal free provided by the invention, environmental-friendly difunctional porous organic frame catalysis material POF-PNA-Br-Tool
Have the advantages that stability is good, is reused many times rear catalytic activity and selectivity is not substantially change.The POF- of the present invention
PNA-Br-Catalysis material is in catalysis CO2Heterogeneous catalysis system is used when carrying out cycloaddition reaction with epoxide, is not required to
Phase synergistic catalyst exists and compared under temperate condition, can efficiently realize CO2With the cycloaddition reaction of epoxide, catalysis production
Rate has many advantages, such as that mild reaction condition, energy conservation and environmental protection, activity are high, selectivity is good, separation is simple up to 98% or more.
Description of the drawings
POF-PN, POF-PNA-Br prepared by Fig. 1 embodiments 1-With the infrared light of two kinds of reactant monomers
Spectrogram comparison diagram；
POF-PN and POF-PNA-Br prepared by Fig. 2 embodiments 1-It is surveyed under 77K, 0~1 atmospheric pressure
Nitrogen adsorption-desorption figure；
POF-PNA-Br prepared by Fig. 3 embodiments 1-Thermal multigraph；
POF-PN and POF-PNA-Br prepared by Fig. 4 embodiments 1-Middle nitrogen x-ray photoelectron spectroscopy
Comparison diagram；
POF-PNA-Br prepared by Fig. 5 embodiments 1-Middle bromo element x-ray photoelectron spectroscopy figure；
POF-PN and POF-PNA-Br prepared by Fig. 6 embodiments 1-XRD spectra；
POF-PN and POF-PNA-Br prepared by Fig. 7 embodiments 1-Scanning electron microscope (SEM) photograph.
Specific implementation mode
In conjunction with attached drawing, present invention is further described in detail with embodiment, it should be pointed out that its purpose is only that more
The protection domain that present disclosure is not intended to limit the present invention is understood well.
Embodiment 1
Step 1：By 0.5mmol tetra- (4- alkynyls tetraphenyl) methane, 1mmol2,5- dibromo pyridines, 0.0075mmol tetra-
(triphenylphosphine) palladium, 0.0075mmol cuprous iodides are dissolved in the in the mixed solvent of 4mL DMF and 2mL triethylamines, reaction system warp
After crossing freezing evacuation nitrogen charging processing three times, it is heated at 60 DEG C and reacts 4 days, obtain mixed liquor.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 3 times, and the organic matter and catalyst that can be dissolved are removed, and 80 DEG C of vacuum are dry under conditions of vacuum degree is 133Pa
Dry 15 hours, obtain the porous organic framework materials POF-PN containing pyridine site.
Step 3：At room temperature, POF-PN described in 1mmol is dispersed in 25mL toluene solutions, in nitrogen protection and stirring
Under the conditions of be added 1.5mmol bromoacetic acids, be heated at 50 DEG C and react 4 days；It is cooled to room temperature, solid product first after filtering
Alcohol, acetone are washed 3 times, are dried in vacuo 15 hours for 80 DEG C, are obtained containing carboxylic acid and bromine anions under conditions of vacuum degree is 133Pa
The difunctional porous organic frame catalysis material POF-PNA-Br in site-。
The POF-PN and POF-PNA-Br that embodiment 1 is synthesized-Structure characterized.
Fig. 1 is POF-PN, POF-PNA-Br prepared by embodiment 1-It is compared with two kinds of organic monomer infrared spectrograms；From figure
1 as can be seen that the c h bond in reaction raw materials four (4- alkynyls tetraphenyl) methane on alkynyl is located at 3280cm-1The stretching vibration at place
It is completely disappeared in POF-PN.In addition, the stretching vibration of C ≡ C is from 2109cm-1It is moved to 2214cm-1, prove two kinds it is organic
Polymerisation occurs for monomer, generates POF-PN.POF-PNA-Br-In 1721cm in infrared spectrum-1There is C=O key characteristic peaks, card
Bright bromoacetic acid is successfully grafted in POF-PN.
Fig. 2 is POF-PN and POF-PNA-Br prepared by embodiment 1-The nitrogen surveyed at 77K and 0~1 atmospheric pressure is inhaled
Attached-desorption figure, typical I- types adsorption isotherm illustrate POF-PN and POF-PNA-Br-With microcellular structure.
Fig. 3 is POF-PNA-Br prepared by embodiment 1-Thermogravimetric test spectrogram, POF-PNA-Br-350 DEG C can be stabilized to,
Illustrate POF-PNA-Br-With good stability.
Fig. 4 is POF-PN and POF-PNA-Br prepared by embodiment 1-Middle nitrogen x-ray photoelectron spectroscopy comparison diagram, card
Bright POF-PNA-Br-The presence of middle azonia.
Fig. 5 is POF-PNA-Br prepared by embodiment 1-Middle bromo element x-ray photoelectron spectroscopy figure, it was demonstrated that POF-PNA-Br-
The presence of middle bromine anions.
Fig. 6 is POF-PN and POF-PNA-Br prepared by embodiment 1-XRD spectra, illustrate POF-PN and POF-PNA-Br-
Crystal structure without long-range order is amorphous material.
Fig. 7 is POF-PN and POF-PNA-Br prepared by embodiment 1-Scanning electron microscope (SEM) photograph；As can be seen from the figure POF-PN
And POF-PNA-Br-It is to be accumulated by regular spherical micron particles.
Study the POF-PNA-Br that embodiment 1 provides-To CO2Catalytic performance；Reaction condition is as follows：POF-PNA-Br-
50mg；Epoxide 1mL；Reaction temperature：40℃；Pressure carbon dioxide：0.1MPa, reaction time are 48 hours.It is catalyzed CO2
Reaction formula with epoxide is：
In R=CH3When, reaction yield 98.5%；
In R=CH2When Cl, reaction yield 94.1%；
In R=CH2CH3When, reaction yield 91.7%；
In R=CH2CH2CH2CH3When, reaction yield 81.2%；The above results show that embodiment 1 provides double without metal
The porous organic frame catalysis material POF-PNA-Br of function-It can be catalyzed under the temperate condition for not needing homogeneous synergistic catalyst
A variety of epoxides and CO2Reaction has good catalytic property.
Embodiment 2
Step 1：By 0.5mmol tetra- (4- alkynyls tetraphenyl) methane, 1mmol2,5- dibromo pyridines, 0.01mmol tetra- (three
Phenylphosphine) palladium, 0.01mmol cuprous iodides be dissolved in the in the mixed solvent of 5mL DMF and 2mL triethylamines, and reaction system is by three times
After freezing evacuates nitrogen charging processing, it is heated at 70 DEG C and reacts 4 days, obtain mixed liquor.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 3 times, and the organic matter and catalyst that can be dissolved are removed, and 90 DEG C of vacuum are dry under conditions of vacuum degree is 133Pa
Dry 12 hours, obtain the porous organic framework materials POF-PN containing pyridine site.
Step 3：At room temperature, POF-PN described in 1mmol is dispersed in 25mL toluene solutions, in nitrogen protection and stirring
Under the conditions of be added 2mmol bromoacetic acids, be heated at 50 DEG C and react 2 days；It is cooled to room temperature, solid product first after filtering
Alcohol, acetone are washed 4 times, are dried in vacuo 12 hours for 90 DEG C, are obtained containing carboxylic acid and bromine anions under conditions of vacuum degree is 133Pa
The difunctional porous organic frame catalysis material POF-PNA-Br in site-。
Study the POF-PNA-Br that embodiment 2 provides-To CO2Catalytic performance；Reaction condition is same as Example 1.
In R=CH3When, reaction yield 96.7%；
In R=CH2When Cl, reaction yield 94.3%；
In R=CH2CH3When, reaction yield 91.1%；
In R=CH2CH2CH2CH3When, reaction yield 78.2%
Embodiment 3
Step 1：By 0.5mmol tetra- (4- alkynyls tetraphenyl) methane, 1.5mmol2,5- dibromo pyridines, 0.015mmol tetra-
(triphenylphosphine) palladium, 0.015mmol cuprous iodides are dissolved in the in the mixed solvent of 6mL DMF and 3mL triethylamines, and reaction system is passed through
After freezing evacuates nitrogen charging processing three times, it is heated at 80 DEG C and reacts 3 days, obtain mixed liquor.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 5 times, and the organic matter and catalyst that can be dissolved are removed, and 100 DEG C of vacuum are dry under conditions of vacuum degree is 133Pa
Dry 12 hours, obtain the porous organic framework materials POF-PN containing pyridine site.
Step 3：At room temperature, POF-PN described in 1mmol is dispersed in 30mL toluene solutions, in nitrogen protection and stirring
Under the conditions of be added 2mmol bromoacetic acids, be heated at 70 DEG C and react 2 days；It is cooled to room temperature, solid product first after filtering
Alcohol, acetone are washed 4 times, are dried in vacuo 12 hours for 100 DEG C under conditions of vacuum degree is 133Pa, obtain containing carboxylic acid and bromine the moon from
The difunctional porous organic frame catalysis material POF-PNA-Br in site of son-。
Study the POF-PNA-Br that embodiment 3 provides-To CO2Catalytic performance；Reaction condition is same as Example 1.
In R=CH3When, reaction yield 97.0%；
In R=CH2When Cl, reaction yield 92.3%；
In R=CH2CH3When, reaction yield 90.2%；
In R=CH2CH2CH2CH3When, reaction yield 77.1%.
Embodiment 4
Step 1：By 0.5mmol tetra- (4- alkynyls tetraphenyl) methane, 2mmol2,5- dibromo pyridines, 0.015mmol tetra- (three
Phenylphosphine) palladium, 0.015mmol cuprous iodides be dissolved in the in the mixed solvent of 8mL DMF and 3mL triethylamines, and reaction system passes through three
After secondary freezing evacuates nitrogen charging processing, it is heated at 90 DEG C and reacts 2 days, obtain mixed liquor.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 5 times, and the organic matter and catalyst that can be dissolved are removed, and 110 DEG C of vacuum are dry under conditions of vacuum degree is 133Pa
Dry 12 hours, obtain the porous organic framework materials POF-PN containing pyridine site.
Step 3：At room temperature, POF-PN described in 1mmol is dispersed in 40mL toluene solutions, in nitrogen protection and stirring
Under the conditions of be added 4mmol bromoacetic acids, be heated at 70 DEG C and react 1 day；It is cooled to room temperature, solid product first after filtering
Alcohol, acetone are washed 5 times, are dried in vacuo 10 hours for 100 DEG C under conditions of vacuum degree is 133Pa, obtain containing carboxylic acid and bromine the moon from
The difunctional porous organic frame catalysis material POF-PNA-Br in site of son-。
Study the POF-PNA-Br that embodiment 4 provides-To CO2Catalytic performance；Reaction condition is same as Example 1.
In R=CH3When, reaction yield 96.6%；
In R=CH2When Cl, reaction yield 92.1%；
In R=CH2CH3When, reaction yield 91.6%；
In R=CH2CH2CH2CH3When, reaction yield 80.3%.
Embodiment 5
Step 1：By 0.5mmol tetra- (4- alkynyls tetraphenyl) methane, 2mmol2,5- dibromo pyridines, 0.015mmol tetra- (three
Phenylphosphine) palladium, 0.015mmol cuprous iodides be dissolved in the in the mixed solvent of 8mL DMF and 4mL triethylamines, and reaction system passes through three
After secondary freezing evacuates nitrogen charging processing, it is heated at 100 DEG C and reacts 1 day, obtain mixed liquor.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrochysene respectively
Tetrahydrofuran solution is washed 5 times, and the organic matter and catalyst that can be dissolved are removed, and 120 DEG C of vacuum are dry under conditions of vacuum degree is 133Pa
Dry 12 hours, obtain the porous organic framework materials POF-PN containing pyridine site.
Step 3：At room temperature, POF-PN described in 1mmol is dispersed in 50mL toluene solutions, in nitrogen protection and stirring
Under the conditions of be added 5mmol bromoacetic acids, be heated at 90 DEG C and react 1 day；It is cooled to room temperature, solid product first after filtering
Alcohol, acetone are washed 5 times, are dried in vacuo 10 hours for 100 DEG C under conditions of vacuum degree is 133Pa, obtain containing carboxylic acid and bromine the moon from
The difunctional porous organic frame catalysis material POF-PNA-Br in site of son-。
Study the POF-PNA-Br that embodiment 5 provides-To CO2Catalytic performance；Reaction condition is same as Example 1.
In R=CH3When, reaction yield 94.7%；
In R=CH2When Cl, reaction yield 90.5%；
In R=CH2CH3When, reaction yield 89.7%；
In R=CH2CH2CH2CH3When, reaction yield 78.2%.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.It for those of ordinary skill in the art, can be according to the present invention
Technical solution and inventive concept, make it is corresponding change and replace, and performance or use is identical, all should be considered as the present invention
Protection domain.
Claims (8)
1. the technical solution adopted by the present invention is to provide a kind of difunctional porous organic frame catalysis material, it is characterized in that by four
Two kinds of organic monomers generation polymerisations of (4- alkynyls tetraphenyl) methane and 2,5- dibromo pyridines connect generation one kind and containing pyridine
The porous organic framework materials in position, modify after then carrying out bromoacetic acid to its pyridine position, obtain containing carboxylic acid site and bromine anions
The difunctional porous organic frame catalysis material in site, the difunctional porous organic frame catalysis material structural formula such as formula (I)
It is shown：
。
2. according to the preparation method of difunctional porous organic frame catalysis material shown in claim 1, which is characterized in that including
Following steps：
Step 1：Four (4- alkynyls tetraphenyl) methane, 2,5- dibromo pyridines, tetrakis triphenylphosphine palladium, cuprous iodide are dissolved in N,
The in the mixed solvent of dinethylformamide (DMF) and triethylamine, reaction system add after freezing evacuate nitrogen charging processing three times
Heat, which is warming up at 60~100 DEG C, reacts 1~4 day, obtains mixed liquor；Four (4- alkynyls tetraphenyl) methane, 2,5- dibromo pyridines, four
(triphenylphosphine) palladium, cuprous iodide, DMF and triethylamine molar ratio be 1:1~4:0.015~0.03:0.015~0.03:100
~300:50~80.
Step 2：The mixed solution filtering that step 1 is obtained, obtained solid product use DMF, water, methanol and tetrahydrofuran respectively
Solution is washed 3~5 times, and the organic matter and catalyst that can dissolve are removed, under conditions of vacuum degree is 133Pa 80~120 DEG C it is true
Sky is 12~15 hours dry, obtains the porous organic framework materials (POF-PN) containing pyridine site.
Step 3：At room temperature, the POF-PN is dispersed in toluene solution, bromine second is added under nitrogen protection and stirring condition
Acid is heated at 50~90 DEG C and reacts 1~4 day；It is cooled to room temperature, solid product methanol, acetone wash 3~5 after filtering
It is secondary, it is dried in vacuo 10~15 hours for 80~100 DEG C, is obtained containing difunctional porous organic under conditions of vacuum degree is 133Pa
Frame catalysis material (POF-PNA-Br-)；The molar ratio of POF-PN, bromoacetic acid and toluene solution are 1:1~5:200~500.
3. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that the step
A rapid reactant is four (4- alkynyls tetraphenyl) methane and 2,5- dibromo pyridines.
4. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that the step
A rapid reaction dissolvent is DMF and triethylamine mixed solvent.
5. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that described four
(4- alkynyls tetraphenyl) methane, 2,5- dibromo pyridines, tetrakis triphenylphosphine palladium, cuprous iodide molar ratio are 1:1~4:0.015~
0.03:0.015~0.03.
6. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that the step
Rapid three solvent for use is toluene.
7. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that the step
Rapid three POF-PN is 1 with bromoacetic acid molar ratio:1~5.
8. the preparation method of difunctional porous organic frame catalysis material according to claim 2, characterized in that the step
Rapid three reaction condition is to be reacted 1~4 day at 50~90 DEG C.
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